CN111655744A - Multimodal ethylene polymer composition with improved toughness - Google Patents

Abstract

Embodiments of polymer compositions and articles including such compositions contain at least one multimodal ethylene polymer having at least three ethylene components, wherein the multimodal ethylene polymer exhibits improved toughness.

Description

Multimodal ethylene polymer composition with improved toughness

Cross Reference to Related Applications

This application claims priority to U.S. provisional application serial No. 62/610,393, filed on 26.12.2017, which is incorporated herein by reference in its entirety.

Technical Field

Embodiments of the present disclosure generally relate to ethylene-based polymer compositions, and more particularly, to multimodal ethylene-based polymer compositions having an excellent balance of toughness and other physical properties.

Background

In monolayer and multilayer films, which may comprise blown or cast films, it is advantageous that the films have excellent physical properties under a variety of different environments and conditions. However, to ensure that the polymer resin has sufficient hardness, a trade-off in toughness is typically required.

Disclosure of Invention

Thus, there is a continuing need for multimodal ethylene-based polymer compositions having improved physical properties. The multimodal ethylene-based polymer of the present invention meets these needs and exhibits an excellent balance of physical properties (e.g., dart drop strength and secant modulus).

In accordance with at least one embodiment of the present disclosure, a polymer composition is provided. The composition comprises at least one multimodal ethylene polymer. In general, the multimodal ethylene-based polymer has a density of from 0.900g/cc to 0.940g/cc when measured in accordance with ASTM D792 and a density of from 2.16 kilograms (kg) when measured at a load of 2.16 kilograms (kg) and a temperature of 190 degrees Celsius (C.) in accordance with ASTM D1238Melt index (I) of the Compound₂) Is 0.1g/10min to 10g/10 min. The multimodal ethylene polymer comprises three ethylene components, wherein the three ethylene components are ethylene monomer and at least one C₃–C₁₂α -polymerization reaction product of an olefin comonomer.

The first ethylene-based component has a density of 0.860 to 0.915g/cc, and a weight average molecular weight (M) of the first ethylene-based component_w(GPC)) From 128,000g/mol to 363,000 g/mol. The multimodal ethylene-based polymer may include at least 20% by weight of the first ethylene-based component. The density of the second ethylene-based component is greater than the density of the first ethylene-based component and less than 0.940g/cc, and the weight average molecular weight (M) of the second ethylene-based component_w(GPC)) From 88,500g/mol to 363,000 g/mol. The density of the third ethylene-based component is greater than the density of the second ethylene-based component.

Finally, according to other embodiments, articles are provided that include the polymer compositions described above.

These and other examples are described in more detail in the detailed description that follows.

Drawings

The following detailed description of specific embodiments of the present disclosure can be best understood when read in conjunction with the following drawings, where like structure is indicated with like reference numerals and in which:

FIG. 1 is a graph depicting 1% secant modulus versus dart drop strength by A for various inventive and comparative monolayer film examples.

Figure 2 is a graphical representation depicting the Crystallization Elution Fraction (CEF) weight fraction versus temperature for inventive polymer 2 and comparative polymer 6.

Figure 3 depicts a side-by-side Short Chain Branching Distribution (SCBD) elution profile and Molecular Weight Distribution (MWD) plot of comparative polymer 7, which was used to estimate the initial parameters of the numerical deconvolution process described below.

Figure 4 shows combined iterations and checks of Short Chain Branching Distribution (SCBD) elution profiles and Molecular Weight Distribution (MWD) plots of inventive polymer 4 by GPC chromatography equipped with an internal IR5 infrared detector (GPC-IR).

Detailed Description

Specific embodiments of the present application will now be described. This disclosure may, however, be embodied in different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the subject matter to those skilled in the art.

Definition of

The term "polymer" refers to a polymeric compound prepared by polymerizing monomers of the same or different types. Thus, the generic term polymer encompasses the term "homopolymer", which is commonly used to refer to polymers prepared from only one type of monomer, as well as the term "copolymer", which refers to polymers prepared from two or more different monomers. As used herein, the term "interpolymer" refers to a polymer prepared by the polymerization of at least two different types of monomers. Thus, the generic term interpolymer encompasses copolymers, as well as polymers prepared from two or more different types of monomers, such as terpolymers.

As used herein, "multimodal" means a composition that can be characterized by having at least three (3) polymer subcomponents of varying density and weight average molecular weight, and optionally, the composition may also have different melt index values. In one embodiment, multimodal may be defined by having at least three distinct peaks in a Gel Permeation Chromatography (GPC) chromatogram showing the molecular weight distribution. In another embodiment, multimodal may be defined by having at least three distinct peaks in a Crystallization Elution Fractionation (CEF) chromatogram showing short chain branching distribution. Multimodal includes resins with three peaks as well as resins with more than three peaks.

The term "trimodal polymer" means a multimodal ethylene-based polymer having three main components: a first ethylene-based polymer component, a second ethylene-based polymer component, and a third ethylene-based polymer component.

As used herein, a "solution polymerization reactor"Is a vessel for carrying out solution polymerization in which ethylene monomer and at least C₃–C₁₂α -olefin comonomer copolymerizes after dissolution in a non-reactive solvent containing a catalyst in a solution polymerization process, hydrogen may be utilized, however, not all solution polymerization processes require hydrogen.

"polyethylene" or "ethylene-based polymer" shall mean a polymer comprising greater than 50 mole percent of units derived from ethylene monomers. This includes ethylene based homopolymers or copolymers (meaning units derived from two or more comonomers). Common forms of ethylenic polymer known in the art include: low Density Polyethylene (LDPE); linear Low Density Polyethylene (LLDPE); ultra Low Density Polyethylene (ULDPE); very Low Density Polyethylene (VLDPE); a single-site catalyzed linear low density polyethylene comprising both a linear low density resin and a substantially linear low density resin (m-LLDPE); medium Density Polyethylene (MDPE); and High Density Polyethylene (HDPE).

"ethylenic component", e.g., "first ethylenic component", "second ethylenic component", or "third ethylenic component", refers to a subcomponent of a multimodal or multimodal polymer in which each subcomponent is a polymer comprising ethylene monomers and C₃–C₁₂α -an ethylene interpolymer of an olefin comonomer.

The term "LDPE" may also be referred to as "high pressure ethylene polymer" or "highly branched polyethylene" and is defined to mean that the polymer is partially or fully homopolymerized or copolymerized in autoclave or tubular reactors at pressures above 14,500psi (100MPa) using free radical initiators (e.g., peroxides) (see, for example, U.S. Pat. No. 4,599,392, which is incorporated herein by reference).

The term "LLDPE" includes resins prepared using Ziegler-Natta (Ziegler-Natta) catalyst systems as well as resins prepared using single site catalysts, including but not limited to dual metallocene catalysts (sometimes referred to as "m-LLDPE"), phosphinimines, constrained geometry catalysts, and resins prepared using post-metallocene molecular catalysts, including but not limited to bis (biphenylphenoxy) catalysts, also referred to as polyvalent aryloxyether catalysts. LLDPE comprises linear, substantially linear or heterogeneous ethylene copolymers or homopolymers. LLDPE contains less long chain branching than LDPE and comprises: a substantially linear ethylene polymer, further defined in U.S. Pat. No. 5,272,236, U.S. Pat. No. 5,278,272, U.S. Pat. No. 5,582,923, and U.S. Pat. No. 5,733,155; homogeneously branched linear ethylene polymer compositions, such as those in U.S. Pat. No. 3,645,992; heterogeneously branched ethylene polymers, such as those prepared according to the methods disclosed in U.S. Pat. No. 4,076,698; and blends thereof (e.g., blends as disclosed in U.S. patent No. 3,914,342 or U.S. patent No. 5,854,045). The LLDPE resin can be prepared by gas phase, solution phase or slurry polymerization, or any combination thereof, using any type of reactor or reactor configuration known in the art.

"multilayer structure" means any structure having more than one layer. For example, the multilayer structure (e.g., film) may have two, three, four, five, or more layers. The multi-layer structure may be described as having layers represented by letters. For example, a three-layer structure having a core layer B and two outer layers a and C may be represented as a/B/C. Also, a structure having two core layers B and C and two outer layers a and D is represented as a/B/C/D. In some embodiments, the multilayer film of the present disclosure comprises up to 11 layers.

Reference will now be made in detail to polymer composition embodiments of the present disclosure, wherein the composition comprises at least one multimodal ethylene-based polymer.

The density of the multimodal ethylene-based polymer may be from 0.900g/cc to 0.940g/cc as measured in accordance with ASTM D792, as previously described. The multimodal ethylene-based polymer may also have a melt index of from 0.1g/10min to 10g/10 min. In further embodiments, the ethylene-based polymer may have a density from 0.910g/cc to 0.940g/cc or from 0.915g/cc to 0.940 g/cc. Further, the multimodal ethylene-based polymer may have a melt index of from 0.1g/10min to 5.0g/10min, or from 0.3g/10min to 2.0g/10min, or from 0.1g/10min to 1.0g/10min, or from 0.5g/10min to 1.0g/10 min. In addition, the first and second substrates are,multimodal ethylene polymers I₁₀/I₂A value of 9 to 15, wherein I₁₀Measured according to ASTM D1238 under a load of 10kg and a temperature of 190 ℃. In further embodiments, I of multimodal ethylene polymers₁₀/I₂From 9 to 14.

The multimodal ethylene polymer comprises ethylene monomer and at least one C₃–C₁₂α -one or more polymerization products of olefin comonomers in another embodiment, C₃–C₁₂α -olefin comonomer may more preferably be from 3 to 8 carbon atoms exemplary α olefin comonomers include, but are not limited to, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, and 4-methyl-1-pentene one or more α -olefin comonomers may be selected from the group consisting of propylene, 1-butene, 1-hexene, and 1-octene, or in the alternative, from the group consisting of 1-butene, 1-hexene, and 1-octene, and further, from 1-hexene, and 1-octene.

For multimodal ethylene polymers, ethylene monomers with C are considered₃–C₁₂α -various levels of incorporation of olefin comonomer for example, a multimodal ethylene polymer may comprise at least 50 mole% ethylene monomer, or at least 60 mole% ethylene monomer, or at least 70 mole% ethylene monomer, or at least 80 mole% ethylene monomer, or at least 90 mole% ethylene monomer, conversely, a multimodal ethylene polymer may comprise less than 50 mole% C₃–C₁₂α -olefin comonomer in further embodiments, the multimodal ethylene-based polymer may include 1 to 40 mole% C₃–C₁₂α -olefin comonomer, or 1 to 30 mol% of C₃–C₁₂α -olefin comonomer, or 1 to 20 mol% of C₃–C₁₂α -olefin comonomer or 1 to 10 mol% of C₃–C₁₂α -olefin comonomer.

The multimodal ethylene polymer comprises at least three ethylene components, each of which is ethylene monomer and at least one C₃–C₁₂α -polymerization reaction product of an olefin comonomer.

In further embodiments, the MWD (M) of the multimodal ethylene polymer_w(GPC)/M_n(GPC)) May be at least 5, or at least 6 or at least 7. In further embodiments, the MWD is 5 to 12, or 6 to 10, or 7 to 9.

The first ethylene-based component has a density of about 0.860g/cc to 0.915g/cc, and the first ethylene-based component has C₃–C₁₂Comonomer incorporation was at least 0.5 mol.%. The density of the ethylene-based components (e.g., the first ethylene-based component, the second ethylene-based component, and the third ethylene-based component) is calculated according to the equation provided below. In another embodiment, the first ethylene-based component has a density from 0.865g/cc to 0.910g/cc, or from 0.870g/cc to 0.905g/cc, or from 0.877g/cc to 0.905 g/cc. Further, in some embodiments, the first ethylene-based component has a melt index (I)₂) Is 0.01g/10min to 0.2g/10min or 0.01g/10min to 0.1g/10 min.

Further, in further embodiments, M of the first ethylene-based component_w(GPC)Can be from 128,000g/mol to 363,000g/mol, or from 150,000g/mol to 360,000g/mol, or from 200,000g/mol to 355,000g/mol or from 225,000g/mol to 350,000 g/mol. In addition, M of the first ethylene component_n(GPC)May be from 100,000g/mol to 200,000g/mol or from 100,000g/mol to 175,000 g/mol. In other embodiments, the MWD (M) of the first ethylene component_w(GPC)/M_n(GPC)) And may be 2.0 to 2.5.

For the first ethylene-based component, C is considered₃–C₁₂α -various additional amounts of olefin comonomer incorporation for example, the first ethylenic component may have a C of 1 to 30 mol%₃–C₁₂α -olefin comonomer or 2 to 20 mol.% C₃-C₁₂α -olefin comonomer.

The density of the second ethylene-based component is greater than the density of the first ethylene-based component and less than 0.940g/cc, and C of the second ethylene-based component₃–C₁₂α -olefin comonomer incorporation of at least 0.5molThe component has a density of from 0.880g/cc to 0.930g/cc, or from 0.890g/cc to 0.930g/cc, or from 0.895g/cc to 0.925 g/cc. Further, in some embodiments, the second ethylene-based component has a melt index from 0.01g/10min to 2g/10min, or from 0.1g/10min to 1.5g/10min, or from 0.2g/10min to 1.0g/10 min.

Further, in further embodiments, M of the second ethylene-based component_w(GPC)May be from 88,000g/mol to 363,000g/mol, or from 100,000g/mol to 200,000g/mol or from 115,000g/mol to 175,000 g/mol. In addition, M of the second ethylene-based component_n(GPC)May be from 50,000g/mol to 90,000g/mol or from 55,000g/mol to 80,000 g/mol. In other embodiments, the MWD (M) of the second ethylene-based component_w/M_n) And may be 2.0 to 2.5.

It is also contemplated that the second ethylene-based component has various levels of C₃–C₁₂α -olefin comonomer incorporation in one embodiment, the second ethylene-based component may have a lower C than the first ethylene-based component₃–C₁₂α -olefin comonomer incorporation for example, the second ethylene-based component may have a C of 0.5 to 40 mol%₃–C₁₂α -olefin comonomer, or 1 to 35 mol.% C₃–C₁₂α -olefin comonomer or 2 to 25 mol.% C₃–C₁₂α -olefin comonomer.

The density of the third ethylene-based component is greater than the density, melt index (I) of the second ethylene-based component₂) Is at least 2.0g/10 min. In further embodiments, the third ethylenic component has a melt index (I)₂) Is 2.0g/10min to 5000g/10min, or 10g/10min to 1000g/10min, or 20g/10min to 750g/10 min. In some embodiments, the third olefinic component has a density from 0.935g/cc to 0.965g/cc, or from 0.945g/cc to 0.965g/cc, or from 0.950g/cc to 0.965 g/cc.

Further, in another embodiment, M of the third ethylenic component_w(GPC)May be less than 88,500g/mol or less than 60,000 g/mol. In further embodiments, M of a third ethylenic component_wMay be from 10,000g/mol to 60,000g/mol or from 15,000g/mol to 50,000 g/mol. In further embodiments, the thirdM of ethylene component_n(GPC)May be from 4,000g/mol to 20,000g/mol or from 4,500g/mol to 15,000 g/mol. In other embodiments, the MWD (M) of the third olefinic component_w(GPC)/M_n(GPC)) May be at least 2.0, or from 2.5 to 6.0 or from 3.0 to 4.5.

The amount of each component in the multimodal ethylene-based polymer may be adjusted based on the application or use. For example, a different balance of properties may be required in low temperature applications (e.g., below 0 ℃) relative to applications where the multimodal ethylene-based polymer is subjected to higher temperatures (e.g., temperatures above 40 ℃). In some embodiments, the multimodal ethylene-based polymer includes from 20 wt% to 40 wt% of the first ethylene-based component or from 20 wt% to 35 wt% of the first ethylene-based component. Additionally, in some embodiments, the multimodal ethylene-based polymer includes from 10 wt% to 40 wt% of the second ethylene-based component or from 15 wt% to 35 wt% of the second ethylene-based component. Further, in some embodiments, the multimodal ethylene polymer includes from 25% to 60% by weight of the third ethylene component or from 35% to 60% by weight of the third ethylene component.

In further embodiments, the multimodal ethylene polymer is at 20 ℃ to T_{Critical point of}(T_c) A Crystallization Elution Fraction (CEF) of more than 23% by weight and a weight average molecular weight (M)_w(CEF)) Greater than 100,000 g/mol. Without being bound by theory, the CEF weight fraction and M are within the temperature range_w(CEF)Such a combination of (a) may indicate that there is more of the lower density first ethylene-based component. In further embodiments, the multimodal ethylene polymer is at 20 ℃ to T_{Critical point of}(T_c) May have a CEF weight fraction of more than 21 wt% and a Mw of more than 125,000g/mol, or from 20 ℃ to T_{Critical point of}(T_c) Has a weight fraction of more than 22 wt% and an Mw of more than 150,000 g/mol.

Various embodiments of the polymerization process are considered suitable for producing multimodal ethylene-based polymers. In one or more embodiments, multimodal ethylene-based polymers are produced by a solution polymerization process in a dual reactor system. These dual solution polymerization reactors may be conventional reactors such as, for example, loop reactors, isothermal reactors, adiabatic reactors and continuous stirred tank reactors in parallel, series, and any combination thereof. In one embodiment, the multimodal ethylene polymer may be produced in two loop reactors configured in series, the first solution polymerization reactor temperature being in the range of 115 ℃ to 200 ℃ (e.g., 135 ℃ to 165 ℃) and the second solution polymerization reactor temperature being in the range of 150 ℃ to 215 ℃ (e.g., 185 ℃ to 202 ℃). In the solution polymerization process, ethylene monomer, one or more C's may be added₃–C₁₂α -olefin comonomer, solvent, catalyst system(s), and optionally hydrogen are continuously fed to a two solution polymerization reactor (i.e., a first solution polymerization reactor and a second solution polymerization reactor).

Various catalysts are deemed suitable. These catalysts may include, but are not limited to, ziegler-natta catalysts, chromium catalysts, metallocene catalysts, post-metallocene catalysts, Constrained Geometry Complex (CGC) catalysts, phosphinimine catalysts, or bis (biphenylphenoxy) catalysts. Details and examples of CGC catalysts are provided in U.S. patent nos. 5,272,236; U.S. Pat. No. 5,278,272; 6,812,289 and WO publication 93/08221, both of which are incorporated by reference herein in their entirety. Details and examples of bis (biphenylphenoxy) catalysts are provided in U.S. Pat. nos. 6,869,904; 7,030,256 No; 8,101,696 No; 8,058,373 No; 9,029,487, the entirety of each of which is incorporated herein by reference. The catalyst used in the solution polymerization reactor may be varied to impart different properties to the first ethylene-based component, the second ethylene-based component, and the third ethylene-based component. For example, it is contemplated that different catalysts may be used in the solution polymerization reactor to vary the density, melt index, comonomer incorporation, etc. of the first ethylene-based component, the second ethylene-based component, and the third ethylene-based component. Without being bound by theory, varying these parameters of the first ethylene-based component, the second ethylene-based component, and the third ethylene-based component can provide the multimodal ethylene-based polymer with a desired combination of toughness and hardness.

In one or more embodiments, the first solution polymerization reactor, the second solution polymerization reactor, or both may contain two catalysts. In particular embodiments, a first solution polymerization reactor may contain two catalysts, and a second solution polymerization reactor located downstream of the first solution polymerization reactor contains one catalyst. Both catalysts of the first solution polymerization reactor are homogeneous catalysts, while the catalyst of the second solution polymerization reactor may comprise a homogeneous catalyst, a heterogeneous catalyst, or both. Homogeneous catalysts (often referred to as single-site catalysts) are organometallic compounds that typically have a discontinuous molecular structure and, in the case of preparing interpolymers, are used to prepare polymers having a narrow molecular weight distribution and a narrow composition distribution. The homogeneous catalyst may be dissolved in a solution process or supported for use in a particle formation process (e.g., slurry or gas phase). Heterogeneous catalysts are not discrete compounds, but result from the metal compound and the precursor being a complex-forming reaction mixture having a plurality of active sites on some form of particle. Polymers produced by homogeneous catalysts generally exhibit a broader molecular weight distribution than homogeneous catalysts, and in the case of interpolymers, a broader composition distribution. In exemplary embodiments, the catalyst in the first reactor may be a different homogeneous catalyst having a different reactivity ratio in the first reactor environment.

Bis (biphenylphenoxy) catalysts are examples of homogeneous catalysts. Other examples of homogeneous catalysts include constrained geometry catalysts. Examples of heterogeneous catalysts may include ziegler-natta catalysts that are particularly useful at the high polymerization temperatures of solution processes. Examples of such Ziegler-Natta catalysts are catalysts derived from organomagnesium compounds, alkyl halides or aluminum halides or hydrogen chloride and transition metal compounds. Examples of such catalysts are described in U.S. patent nos. 4,314,912 (Lowery, Jr et al), 4,547,475 (Glass et al) and 4,612,300 (Coleman, III), the teachings of which are incorporated herein by reference.

Particularly suitable organomagnesium compounds include, for example, hydrocarbon-soluble dihydrocarbylmagnesium, such as dialkylmagnesium and diarylmagnesium. Exemplary suitable magnesium dialkyls include, in particular, n-butyl-sec-butylmagnesium, diisopropylmagnesium, di-n-hexylmagnesium, isopropyl-n-butylmagnesium, ethyl-n-hexylmagnesium, ethyl-n-butylmagnesium, di-n-octylmagnesium, and other magnesium dialkyls wherein the alkyl group has from 1 to 20 carbon atoms. Exemplary suitable diarylmagnesium include diphenylmagnesium, dibenzylmagnesium, and ditolylmesium. Suitable organomagnesium compounds include alkoxides and phenoxides of alkyl and aryl magnesium and halides of aryl and alkyl magnesium, with halogen-free organomagnesium compounds being more preferred.

The bis (biphenylphenoxy) catalyst is a multi-component catalyst system comprising a bis (biphenylphenoxy) procatalyst, a cocatalyst and further optional ingredients. The bis (biphenylphenoxy) procatalyst may comprise a metal-ligand complex according to formula (I):

in formula (I), M is a metal selected from titanium, zirconium or hafnium, said metal being in an apparent oxidation state of +2, +3 or + 4; n is 0, 1 or 2; when n is 1, X is a monodentate ligand or a bidentate ligand; when n is 2, each X is a monodentate ligand and is the same or different; the metal-ligand complex is generally charge neutral; o is O (oxygen atom); each Z is independently selected from-O-, -S-, -N (RN) -or-P (R)^P) -; l is (C)₁-C₄₀) Alkylene or (C)₁-C₄₀) A heterohydrocarbylene group of which (C)₁-C₄₀) The alkylene group has a moiety (bonded to L) or (C) comprising a 1-to 10-carbon atom linking backbone linking two Z groups in formula (I)₁-C₄₀) The heterohydrocarbylene group has a moiety comprising a 1-atom to 10-atom linking backbone linking two Z groups in formula (I) wherein (C)₁-C₄₀) Each of the 1-atom to 10-atom linking atoms in the backbone of the heteroalkylene is independently a carbon atom or a heteroatom, wherein each heteroatom is independently O, S, S (O), S (O)2, Si (R)^C)2、Ge(R^C)2、P(R^C) Or N (R)^C) Which isEach R in^CIndependently is (C1-C30) hydrocarbyl or (C)₁-C₃₀) A heterohydrocarbyl group; r¹And R⁸Independently selected from the group consisting of: (C)₁-C₄₀) Hydrocarbyl radical, (C)₁-C₄₀) Heterohydrocarbyl, -Si (R)^C)₃、-Ge(R^C)₃、-P(R^P)₂、-N(R^N)₂、-OR^C、-SR^C、-NO₂、-CN、-CF₃、R^CS(O)-、R^CS(O)₂-、(R^C)₂C＝N-、R^CC(O)O-、R^COC(O)-、R^CC(O)N(R^N)-、(R^N)₂Nc (o) -, halogen and a group having formula (II), formula (III) or formula (IV):

in the formulae (II), (III) and (IV), R^31–35、R^41–48Or R^51–59Each of (A) is independently selected from (C)₁–C₄₀) Hydrocarbyl radical, (C)₁–C₄₀) Heterohydrocarbyl, -Si (R)^C)₃、-Ge(R^C)₃、-P(R^P)₂、-N(R^N)₂、-OR^C、-SR^C、-NO₂、-CN、-CF₃、R^CS(O)-、R^CS(O)₂-、(R^C)₂C＝N-、R^CC(O)O-、R^COC(O)-、R^CC(O)N(R^N)-、(R^N)₂NC (O) -, halogen or-H, with the proviso that R¹Or R⁸Is a group having formula (II), formula (III) or formula (IV).

In the formula (I), R^2–4、R^5–7And R^9–16Each of (A) is independently selected from (C)₁-C₄₀) Hydrocarbyl radical, (C)₁-C₄₀) Heterohydrocarbyl, -Si (R)^C)₃、-Ge(R^C)₃、-P(R^P)₂、-N(R^N)₂-OR^C、-SR^C、-NO₂、-CN、-CF₃、R^CS(O)-、R^CS(O)₂-、(R^C)₂C＝N-、R^CC(O)O-、R^COC(O)-、R^CC(O)N(R^N)-、(R^C)₂NC (O) -, halogen and-H.

Specific examples of catalyst systems will now be described. It is to be understood that the catalyst systems of the present disclosure may be embodied in different forms and should not be construed as limited to the particular embodiments set forth in the disclosure. Rather, embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the subject matter to those skilled in the art.

The term "independently selected" is used herein to indicate an R group (e.g., R)¹、R²、R³、R⁴And R⁵) May be the same or different (e.g., R)¹、R²、R³、R⁴And R⁵May each be substituted alkyl, or R¹And R²May be substituted alkyl and R³May be aryl, etc.). Use of the singular includes use of the plural and vice versa (e.g., a hexane solvent includes a plurality of hexanes). The named R group will generally have a structure recognized in the art as corresponding to the R group having the name. These definitions are intended to supplement and illustrate, but not to exclude, definitions known to those skilled in the art.

The term "procatalyst" refers to a compound that has catalytic activity when combined with an activator. The term "activator" refers to a compound that chemically reacts with a procatalyst in a manner that converts the procatalyst into a catalytically active catalyst. As used herein, the terms "cocatalyst" and "activator" are interchangeable terms.

When used to describe certain chemical groups containing carbon atoms, the form is "(C)_x–C_y) By insertional expression "is meant that the unsubstituted form of the chemical group has from x carbon atoms to y carbon atoms, inclusive of x and y. For example, (C)₁–C₄₀) Alkyl is in unsubstituted form having from 1 to 40 carbon atomsAn alkyl group of (2). In some embodiments and general structures, certain chemical groups may be substituted with one or more substituents (e.g., R)^S) And (4) substitution. Using the insert word "(C)_x–C_y) "chemical group defined by R^SThe substituted version may contain more than y carbon atoms depending on any group R^SThe identity of (c). For example, "with only one R^SRadical substituted (C)₁–C₄₀) Alkyl radical, wherein R^SIs phenyl (-C)₆H₅) "may contain 7 to 46 carbon atoms. Therefore, in general, when the insert word "(C) is used_x–C_y) "chemical groups defined by one or more substituents R containing carbon atoms^SWhen substituted, by adding both x and y to the substituents R from all carbon-containing atoms^STo determine the minimum and maximum total number of carbon atoms for the chemical group.

In some embodiments, each of the chemical groups (e.g., X, R, etc.) of the metal-ligand complex of formula (I) may be unsubstituted such that no R is present^SAnd (4) a substituent. In other embodiments, at least one of the chemical groups of the metal-ligand complex of formula (I) may independently contain one or more than one R^S. In some embodiments, R in the chemical group of the metal-ligand complex of formula (I)^SDoes not exceed 20 in total. In other embodiments, R in the chemical group^SDoes not exceed 10 in total. For example, if R^1–5Each with two R^SSubstituted, then X and Z cannot be replaced by R^SAnd (4) substitution. In another embodiment, R in the chemical group of the metal-ligand complex of formula (I)^SMay not exceed 5R^S. When two or more than two R are present^SEach R is bound to the same chemical group of the metal-ligand complex of formula (I)^SIndependently to the same or different carbon or heteroatom and may contain full substitution of chemical groups (persistence).

The term "substituted" means at least one hydrogen atom (-H) By substituents (e.g. R)^S) And (6) replacing. The term "fully substituted" means that each hydrogen atom (H) bound to a carbon atom or heteroatom in the corresponding unsubstituted compound or functional group is substituted (e.g., R)^S) And (6) replacing. The term "polysubstituted" means that at least two (but less than all) hydrogen atoms bound to a carbon atom or a heteroatom in a corresponding unsubstituted compound or functional group are replaced by a substituent.

The term "-H" means a hydrogen or hydrogen group covalently bonded to another atom. "hydrogen" and "-H" are interchangeable and mean the same thing unless explicitly specified.

Term "(C)₁–C₄₀) The hydrocarbon group "means a hydrocarbon group having 1 to 40 carbon atoms, and the term" (C)₁–C₄₀) By hydrocarbylene "is meant a hydrocarbon diradical having 1 to 40 carbon atoms wherein each hydrocarbyl group and each hydrocarbon diradical is aromatic or non-aromatic, saturated or unsaturated, straight or branched chain, cyclic (including monocyclic and polycyclic, fused and non-fused polycyclic, including bicyclic; 3 carbon atoms or more) or acyclic, and unsubstituted or substituted by one or more R^SAnd (4) substitution.

In the present disclosure, (C)₁–C₄₀) The hydrocarbyl groups are independently unsubstituted or substituted (C)₁-C₄₀) Alkyl, (C)₃-C₄₀) Cycloalkyl group, (C)₃–C₂₀) Cycloalkyl- (C)₁-C₂₀) Alkylene, (C)₆-C₄₀) Aryl or (C)₆-C₂₀) Aryl radical- (C)₁-C₂₀) An alkylene group. In some embodiments, the foregoing (C)₁-C₄₀) Each of the hydrocarbon groups has up to 20 carbon atoms (i.e., (C)₁–C₂₀) Hydrocarbyl), and in other embodiments, up to 12 carbon atoms.

Term "(C)₁–C₄₀) Alkyl "and" (C)₁–C₁₈) Alkyl "means a saturated, linear or branched hydrocarbon radical having from 1 to 40 carbon atoms or from 1 to 18 carbon atoms, respectively, said hydrocarbon radical being unsubstituted or substituted by one or more R^SAnd (4) substitution. Is not takenSubstituted (C1-C)₄₀) Examples of alkyl groups are unsubstituted (C)₁–C₂₀) An alkyl group; unsubstituted (C)₁–C₁₀) An alkyl group; unsubstituted (C)₁-C₅) An alkyl group; a methyl group; an ethyl group; 1-propyl group; 2-propyl; 1-butyl; 2-butyl; 2-methylpropyl; 1, 1-dimethylethyl; 1-pentyl; 1-hexyl; 1-heptyl; 1-nonyl; and a 1-decyl group. Substituted (C)₁-C₄₀) Examples of alkyl groups are substituted (C)₁–C₂₀) Alkyl, substituted (C)₁–C₁₀) Alkyl, trifluoromethyl and [ C₄₅]An alkyl group. The term "[ C ]₄₅]alkyl "(with square brackets) means that up to 45 carbon atoms are present in the group (including the substituents) and is, for example, each bound to an R^SSubstituted (C)₂₇–C₄₀) Alkyl radical, said R^SIs (C)₁–C₅) An alkyl group. Each (C)₁–C₅) The alkyl group may be methyl, trifluoromethyl, ethyl, 1-propyl, 1-methylethyl or 1, 1-dimethylethyl.

Term "(C)₆–C₄₀) Aryl "means unsubstituted or substituted with (one or more R) having from 6 to 40 carbon atoms^S) A substituted monocyclic, bicyclic or tricyclic aromatic hydrocarbon group, at least 6 to 14 of the carbon atoms of said aromatic hydrocarbon group being aromatic ring carbon atoms, and said monocyclic, bicyclic or tricyclic group comprising 1,2 or 3 rings, respectively; wherein 1 ring is aromatic and 2 or 3 rings are independently fused or non-fused and at least one of the 2 or 3 rings is aromatic. Unsubstituted (C)₆–C₄₀) Examples of aryl radicals are unsubstituted (C)₆–C₂₀) Aryl, unsubstituted (C)₆–C₁₈) An aryl group; 2- (C)₁-C₅) Alkyl-phenyl; 2, 4-bis (C)₁–C₅) Alkyl-phenyl; a phenyl group; a fluorenyl group; a tetrahydrofluorenyl group; indacene base; hexahydro indacenyl; an indenyl group; a dihydroindenyl group; a naphthyl group; tetrahydronaphthyl; and phenanthrene. Substituted (C)₆–C₄₀) Examples of aryl radicals are substituted (C)₁–C₂₀) An aryl group; substituted (C)₆-C₁₈) An aryl group; 2, 4-bis [ (C)₂₀) Alkyl radical]-a phenyl group; a polyfluorophenyl group; pentafluorophenyl; and fluoren-9-on-l-yl.

Term "(C)₃–C₄₀) Cycloalkyl "means unsubstituted or substituted by one or more R having from 3 to 40 carbon atoms^SSubstituted saturated cyclic hydrocarbyl. Other cycloalkyl groups (e.g., (C)_x–C_y) Cycloalkyl) is defined in an analogous manner as having x to y carbon atoms and being unsubstituted or substituted with one or more R^SAnd (3) substituted. Unsubstituted (C)₃–C₄₀) Examples of cycloalkyl are unsubstituted (C)₃–C₂₀) Cycloalkyl, unsubstituted (C)₃-C₁₀) Cycloalkyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, and cyclodecyl. Substituted (C)₃–C₄₀) Examples of cycloalkyl are substituted (C)₃-C₂₀) Cycloalkyl, substituted (C)₃–C₁₀) Cycloalkyl, cyclopentanone-2-yl and 1-fluorocyclohexyl.

(C₁–C₄₀) Examples of the alkylene group include unsubstituted or substituted (C)₆-C₄₀) Arylene, (C)₃–C₄₀) Cycloalkylene and (C)₁–C₄₀) Alkylene (e.g., (C)₁–C₂₀) Alkylene). In some embodiments, the diradicals are located on the same carbon atom (e.g., -CH)₂-) either on adjacent carbon atoms (i.e., a 1, 2-diradical) or spaced one, two, or more than two intervening carbon atoms apart (e.g., a 1, 3-diradical, a 1, 4-diradical, etc.)₂–C₂₀) Some examples of alkylene α, omega-diyl groups include ethyl-1, 2-diyl (i.e., -CH)₂CH₂) Propane-1, 3-diyl (i.e. -CH)₂CH₂CH₂-), 2-methylpropan-1, 3-diyl (i.e. -CH₂CH(CH₃)CH₂–)。(C₆–C₄₀) Some examples of arylene α, omega-diyl groups include phenyl-1, 4-diyl, naphthalene-2, 6-diyl, or naphthalene-3, 7-diyl.

Term "(C)₁–C₄₀) Alkylene "means unsubstituted or substituted by one or more R having from 1 to 40 carbon atoms^SSubstituted saturated straight or branched chain diradicals (i.e., the diradicals are not on a ring atom). Unsubstituted (C)₁–C₄₀) Examples of alkylene are unsubstituted (C)₁-C₂₀) Alkylene radicals containing unsubstituted-CH₂CH₂-、-(CH₂)₃-、-(CH₂)₄-,-(CH₂)₅-、-(CH₂)₆-,-(CH₂)₇-、-(CH₂)₈-,-CH₂C*HCH₃And- (CH)₂)₄C*(H)(CH₃) Wherein "C" represents a carbon atom from which a hydrogen atom is removed to form a secondary or tertiary alkyl group. Substituted (C)₁–C₄₀) Examples of alkylene groups are substituted (C)₁–C₂₀) Alkylene, -CF₂-, -C (O) -and- (CH)₂)₁₄C(CH₃)₂(CH₂)₅- (i.e., 6, 6-dimethyl-substituted n-1, 20-eicosene). Since, as mentioned above, two R are^SCan be combined to form (C)₁–C₁₈) Alkylene, substituted (C)₁–C₄₀) Examples of alkylene groups also include l, 2-bis (methylene) cyclopentane, 1, 2-bis (methylene) cyclohexane, 2, 3-bis (methylene) -7, 7-dimethyl-bicyclo [2.2.1]Heptane and 2, 3-bis (methylene) bicyclo [2.2.2]Octane.

Term "(C)₃–C₄₀) Cycloalkylene "means unsubstituted or substituted with one or more R having from 3 to 40 carbon atoms^SSubstituted cyclic diradicals (i.e., the diradicals are on a ring atom).

The term "heteroatom" refers to an atom other than hydrogen or carbon. Examples of groups containing one or more than one heteroatom include O, S, S (O), S (O)₂、Si(R^C)₂、P(R^P)、N(R^N)、–N＝C(R^C)₂、-Ge(R^C)₂-or-Si (R)^C) -, wherein each R^CAnd each R^PIs unsubstituted (C)₁-C₁₈) A hydrocarbyl group or-H, and wherein each R^NIs unsubstituted (C)₁-C₁₈) A hydrocarbyl group. The term "heterohydrocarbon" refers to a molecule or molecular backbone having one or more carbon atoms replaced with a heteroatom. Term "(C)₁–C₄₀) Heterohydrocarbyl "means a heterohydrocarbyl group having 1 to 40 carbon atoms, and the term" (C)₁-C₄₀) Heterohydrocarbylene "means a heterohydrocarbyl diradical having 1 to 40 carbon atoms, and each heterohydrocarbyl has one or more heteroatoms. The group of heterohydrocarbyl groups is located on a carbon atom or a heteroatom, and the diradical of heterohydrocarbyl groups may be located: (1) one or two carbon atoms, (2) one or two heteroatoms, or (3) one carbon atom and a heteroatom. Each (C)₁-C₄₀) A heterohydrocarbyl radical and (C)₁–C₄₀) The heterohydrocarbylene group may be unsubstituted or substituted with (one or more R)^S) Substituted, aromatic or non-aromatic, saturated or unsaturated, straight or branched, cyclic (including monocyclic and polycyclic, fused and non-fused polycyclic) or acyclic.

(C₁–C₄₀) The heterocarbyl group may be unsubstituted or substituted. (C)₁–C₄₀) Non-limiting examples of heterocarbyl groups include (C)₁–C₄₀) Heteroalkyl group, (C)₁–C₄₀) alkyl-O-, (C)₁–C₄₀) alkyl-S-, (C)₁–C₄₀) alkyl-S (O) -, (C)₁–C₄₀) alkyl-S (O)₂-、(C₁-C₄₀) hydrocarbyl-Si (R)^C)₂-、(C_l–C₄₀) hydrocarbyl-N (R)^N)-、(C_l–C₄₀) hydrocarbyl-P (R)^P)-、(C₂-C₄₀) Heterocycloalkyl group, (C)₂–C₁₉) Heterocycloalkyl- (C)₁–C₂₀) Alkylene, (C)₃–C₂₀) Cycloalkyl- (C)₁-C₁₉) Heteroalkylene, (C)₂–C₁₉) Heterocycloalkyl- (C)₁–C₂₀) Heteroalkylene, (C)₁–C₅₀) Heteroaryl, (C)₁-C₁₉) Heteroaryl- (C)₁–C₂₀) Alkylene, (C)₆–C₂₀) Aryl radical- (C)₁–C₁₉) Heteroalkylene or (C)₁–C₁₉) Heteroaryl- (C)₁–C₂₀) A heteroalkylene group.

Term "(C)₁–C₄₀) Heteroaryl "means a monocyclic, bicyclic or tricyclic heteroaromatic hydrocarbon group having a total number of carbon atoms of 4 to 40 and a total number of heteroatoms of 1 to 10, unsubstituted or substituted by (one or more RS), and which monocyclic, bicyclic or tricyclic groups include 1,2 or 3 rings, respectively; wherein 2 or 3 rings are independently fused or non-fused and at least one of the 2 or 3 rings is heteroaromatic. Other heteroaryl groups (e.g., typically are (C)_x–C_y) Heteroaryl, e.g. (C)₁–C₁₂) Heteroaryl) is defined in an analogous manner as having x to y carbon atoms (e.g., 1 to 12 carbon atoms) and is unsubstituted or substituted with one or more than one R^SAnd (3) substituted. The monocyclic heteroaromatic hydrocarbon group is a 5-or 6-membered ring. The 5 membered ring has 5 minus h carbon atoms, where h is the number of heteroatoms, and can be 1,2, or 3; and each heteroatom may be O, S, N or P. Examples of 5-membered heteroaromatic hydrocarbon groups are pyrrol-1-yl; pyrrol-2-yl; furan-3-yl; thiophen-2-yl; pyrazol-1-yl; isoxazol-2-yl; isothiazol-5-yl; imidazol-2-yl; oxazol-4-yl; thiazol-2-yl; 1,2, 4-triazol-1-yl; 1,3, 4-oxadiazol-2-yl; 1,3, 4-thiadiazol-2-yl; tetrazol-1-yl; tetrazol-2-yl; and tetrazol-5-yl. The 6 membered ring has 6 minus h carbon atoms, where h is the number of heteroatoms and can be 1 or 2, and the heteroatoms can be N or P. Examples of 6-membered heteroaromatic hydrocarbon groups are pyridin-2-yl; pyrimidin-2-yl; and pyrazin-2-yl. The bicyclic heteroaromatic hydrocarbon group may be a fused 5, 6-or 6, 6-ring system. Examples of fused 5, 6-ring system bicyclic heteroaromatic hydrocarbon radicals are indol-1-yl; and benzimidazol-1-yl. Examples of fused 6, 6-ring system bicyclic heteroaromatic hydrocarbon radicals are quinolin-2-yl; and isoquinolin-1-yl. The bicyclic heteroaromatic hydrocarbon group may be a fused 5,6, 5-ring system; a 5,6, 6-ring system; a 6,5, 6-ring system or a 6,6, 6-ring system. An example of a fused 5,6, 5-ring system is 1, 7-dihydropyrrolo [3,2-f ]]Indol-1-yl. Condensed withAn example of a 5,6, 6-ring system of (a) is 1H-benzo [ f [ -f ]]Indol-1-yl. An example of a fused 6,5, 6-ring system is 9H-carbazol-9-yl. An example of a fused 6,6, 6-ring system is acridin-9-yl.

The aforementioned heteroalkyl group may be a heteroalkyl group containing (C)₁–C₄₀) Saturated straight or branched chain groups of carbon atoms or less and one or more heteroatoms. Likewise, heteroalkylene groups can be saturated straight or branched chain diradicals containing 1 to 50 carbon atoms and one or more than one heteroatom. As defined above, the heteroatom may comprise Si (R)^C)₃、Ge(R^C)₃、Si(R^C)₂、Ge(R^C)₂、P(R^P)₂、P(R^P)、N(R^N)₂、N(R^N)、N、O、OR^C、S、SR^CS (O) and S (O)₂Wherein each of heteroalkyl and heteroalkylene is unsubstituted or substituted with one or more R^SAnd (3) substituted.

Unsubstituted (C)₂–C₄₀) Examples of heterocycloalkyl are unsubstituted (C)₂-C₂₀) Heterocycloalkyl, unsubstituted (C)₂–C₁₀) Heterocycloalkyl, aziridin-l-yl, oxetan-2-yl, tetrahydrofuran-3-yl, pyrrolidin-l-yl, tetrahydrothiophen-S, S-dioxo-2-yl, morpholin-4-yl, 1, 4-dioxan-2-yl, hexahydroazepin-4-yl, 3-oxa-cyclooctyl, 5-thio-cyclononyl and 2-aza-cyclodecyl.

The term "halogen atom" or "halogen" means a group of fluorine atom (F), chlorine atom (Cl), bromine atom (Br) or iodine atom (I). The term "halide" means the anionic form of the halogen atom: fluoride (F)^-) Chloride (Cl)^-) Bromide (Br)^-) Or iodide (I)^-)。

The term "saturated" means lacking carbon-carbon double bonds, carbon-carbon triple bonds and (in heteroatom-containing groups) carbon-nitrogen double bonds, carbon-phosphorus double bonds and carbon-silicon double bonds. When the saturated chemical group is substituted by one or more substituents R^SWhen substituted, one or more double and/or triple bonds may or may not optionally be present in the substituent R^SIn (1). The term "unsaturated" means containing one or more carbon-carbon double bonds, carbon-carbon triple bonds and (in heteroatom-containing groups) carbon-nitrogen double bonds, carbon-phosphorus double bonds and carbon-silicon double bonds, and does not contain any substituents which may be present in the substituents R^SIf any, or any double bonds present in the (hetero) aromatic ring (if any).

In some embodiments, the catalyst system comprising the metal-ligand complex of formula (I) may be made catalytically active by any technique known in the art for activating metal-based catalysts for olefin polymerization reactions. For example, a catalyst system comprising a metal-ligand complex of formula (I) can be made catalytically active by contacting the complex with an activating cocatalyst or combining the complex with an activating cocatalyst. Suitable activating cocatalysts for use herein comprise an aluminum alkyl; polymeric or oligomeric aluminoxanes (also known as aluminoxanes); a neutral lewis acid; and non-polymeric, non-coordinating ion-forming compounds (including the use of such compounds under oxidizing conditions). A suitable activation technique is bulk electrolysis (bulk electrolysis). Combinations of one or more of the foregoing activating cocatalysts and techniques are also contemplated. The term "alkylaluminum" means a monoalkylaluminum dihalide or monoalkylaluminum dihalide, a dialkylaluminum hydride or a dialkylaluminum halide or a trialkylaluminum. Examples of the polymeric or oligomeric aluminoxane include methylaluminoxane, methylaluminoxane modified with triisobutylaluminum, and isobutylaluminoxane.

The Lewis acid activator (cocatalyst) comprises a catalyst comprising 1 to 3 of (C) as described herein₁–C₂₀) A hydrocarbyl-substituted group 13 metal compound. In one embodiment, the group 13 metal compound is tris ((C)₁–C₂₀) Hydrocarbyl-substituted aluminium or tris ((C)₁–C₂₀) Hydrocarbyl) -boron compounds. In other embodiments, the group 13 metal compound is a tri (hydrocarbyl) -substituted aluminum, tri (hydrocarbyl) -boron compound, tri ((C)₁–C₁₀) Alkyl) aluminum, tris ((C)₆–C₁₈) Aryl) boron compounds and halogenated (including perhalogenated) derivatives thereof. In further embodiments, group 13 metal compoundsThe compound is tri (fluoro substituted phenyl) borane or tri (pentafluorophenyl) borane. In some embodiments, the activating cocatalyst is tetrakis ((C)₁-C₂₀) Hydrocarbyl) borates (e.g. trityltetrafluoroborate) or tris ((C)₁-C₂₀) Hydrocarbyl) ammonium tetrakis ((C)₁–C₂₀) Hydrocarbyl) boranes (e.g., bis (octadecyl) methylammonium tetrakis (pentafluorophenyl) borane). As used herein, the term "ammonium" is intended as ((C)₁–C₂₀) Alkyl radical)₄N⁺、((C₁-C₂₀) Alkyl radical)₃N(H)⁺、((C₁–C₂₀) Alkyl radical)₂N(H)₂ ⁺、(C₁–C₂₀) Alkyl radicals N (H)₃ ⁺Or N (H)₄ ⁺Of each (C)₁–C₂₀) The hydrocarbyl groups (when two or more are present) may be the same or different.

The combination of neutral lewis acid activators (co-catalysts) comprises a mixture including tris ((C)₁–C₄) Alkyl) aluminium with halogenated tris ((C)₆–C₁₈) Aryl) boron compounds, especially tris (pentafluorophenyl) borane. Other examples are the combination of such neutral lewis acid mixtures with polymeric or oligomeric alumoxanes, and the combination of a single neutral lewis acid, especially tris (pentafluorophenyl) borane, with polymeric or oligomeric alumoxanes. (Metal-ligand Complex) (tris (pentafluorophenyl) borane): an (aluminoxane) [ e.g., (group 4 metal-ligand Complex) (tris (pentafluorophenyl) borane): an (aluminoxane)]In a molar ratio of 1:1:1 to 1:10:30, and in other embodiments 1:1:1.5 to 1:5: 10.

The catalyst system comprising the metal-ligand complex of formula (I) can be activated to form an active catalyst composition by combination with one or more cocatalysts (e.g., cation-forming cocatalysts, strong lewis acids, or combinations thereof). Suitable activating cocatalysts include polymeric or oligomeric aluminoxanes, especially methylaluminoxane, and inert, compatible, non-coordinating, ion-forming compounds. Exemplary suitable cocatalysts include, but are not limited to: modified methyl groupAlumoxane (MMAO), bis (hydrogenated tallow alkyl) methyl, tetrakis (pentafluorophenyl) borate (1)^-) Amines and combinations thereof.

In some embodiments, one or more of the foregoing activating cocatalysts are used in combination with each other. A particularly preferred combination is tris ((C)₁-C₄) Hydrocarbyl aluminum, tris ((C)₁–C₄) Hydrocarbyl) borane or ammonium borate with oligomeric or polymeric aluminoxane compounds. The ratio of the total moles of the one or more metal-ligand complexes of formula (I) to the total moles of the one or more activating cocatalysts is from 1:10,000 to 100: 1. In some embodiments, the ratio is at least 1:5000, in some other embodiments, at least 1: 1000; and 10:1 or less, and in some other embodiments, 1:1 or less. When an aluminoxane is used alone as the activating cocatalyst, the number of moles of the aluminoxane employed is preferably at least 100 times the number of moles of the metal-ligand complex of formula (I). In some other embodiments, when tris (pentafluorophenyl) borane is used alone as the activating cocatalyst, the ratio of moles of tris (pentafluorophenyl) borane employed to the total moles of the one or more metal-ligand complexes of formula (I) is 0.5:1 to 10:1, 1:1 to 6:1, or 1:1 to 5: 1. The remaining activating cocatalyst is generally employed in a molar amount approximately equal to the total molar amount of the one or more metal-ligand complexes of formula (I).

Various solvents are contemplated, for example, aromatic solvents and paraffinic solvents. Exemplary solvents include, but are not limited to, isoparaffins. For example, such isoparaffinic solvents are commercially available from exxonmobil chemical under the name ISOPAR E.

The reaction rate is determined by the ethylene and C in the polymerization process₃-C₁₂α -olefin and polymerization catalyst, it is believed that the difference between the polymerization rates (i.e., selectivities) of the olefins and α -olefin (e.g., C)₃-C₁₂α -olefin) results in the polymerization of ethylene being more selective (i.e., the catalyst preferentially polymerizes ethylene in the presence of α -olefin)Resulting in the catalyst (e.g., a homogeneous catalyst prepared with or from the metal-ligand complex of formula (I)) adopting a conformation that substantially more readily brings ethylene into proximity to M, or adopting a more reactive conformation, or both (as compared to a catalyst that allows α -olefin to approach or react with M).

A terminal copolymerization model is used for random copolymers in which the identity of the last monomer inserted determines the subsequent monomer insertion rate. In this model, the type of insertion reaction is

Wherein, C^*Denotes a catalyst, M_iRepresents a monomer i, and k_ijIs a rate constant with a rate equation

The comonomer mole fraction (i ═ 2) in the reaction medium is defined by the following equation:

simplified equations for comonomer compositions can be derived as disclosed in George Odian, Principles of Polymerization (Principles of Polymerization), second edition, John Wiley parent-son press (John Wiley and Sons),1970, as follows:

for this equation, the mole fraction of comonomer in the polymer depends only on the mole fraction of comonomer in the reaction medium and two temperature-dependent reactivity ratios defined in terms of insertion rate constants, as follows:

also for this model, the polymer composition is a function of only the temperature-dependent reactivity and the comonomer mole fraction in the reactor. This is also true when reverse comonomer or monomer insertion is possible, or where more than two monomers are copolymerized.

Well known theoretical techniques can be used to predict the reaction rates used in the aforementioned models, or empirically derived from actual polymerization data. Suitable theoretical techniques are disclosed, for example, in b.g. kyle, "Chemical and Process Thermodynamics (Chemical and Process Thermodynamics"), third edition, pentists Hall press (prenotice-Hall), 1999; and Redlich-Kwong-Soave (RKS) equation of state, Chemical Engineering Science (Chemical Engineering Science), 1972, pages 1197-. Commercially available software programs can be used to help derive the reaction rate from the experimentally derived data. An example of such software is Aspen Plus from Aspen Technology, Inc., Ten canal parks, Cambridge 2201, 02141, Mass.

As noted above, embodiments of the present compositions comprising a multimodal ethylene-based polymer and optionally LDPE can be incorporated into a film. The film may be a monolayer or multilayer film produced by blown film or cast film processes. The films may be incorporated into a variety of articles including, for example, food packaging, industrial and consumer packaging materials, architectural films, foam films, and the like.

Optionally, the film may further comprise one or more additives. Additives include, but are not limited to, antistatic agents, colorants, dyes, lubricants, fillers (e.g., TiO)₂Or CaCO₃) An opacifying agent, a nucleating agent, a processing aid, a pigment, a primary antioxidant, a secondary antioxidant, a UV stabilizer, an anti-blocking agent, a slip agent, a tackifier, a flame retardant, an antimicrobial agent, an odor reducing agent, an antifungal agent, and combinations thereof.

In some embodiments, the film is a blown monolayer film having improved toughness, e.g., as evidenced by improved dart drop strength and secant modulus.

Test method

The test method comprises the following steps:

_{2 10}melt indices (I) and (I)

Melt index (I) of multimodal ethylene polymers measured according to ASTM D1238 at 190 ℃ and 2.16kg₂) The value is obtained. Similarly, the melt index (I) of a multimodal ethylene polymer was measured at 190 ℃ and 10kg according to ASTM D1238₁₀) The value is obtained. Values are reported in grams/10 min, which corresponds to the number of grams eluted per 10 min. The melt index (I) of the first ethylene-based component, the second ethylene-based component and the third ethylene-based component was calculated according to equation 30 and the method described below₂) The value is obtained.

Density of

Density measurements of multimodal ethylene polymers were made according to ASTM D792, method B. For the first ethylene-based component and the second ethylene-based component, density values were obtained using equation 28 and the method described below. For the third vinyl component, density values were calculated using equation 29.

Conventional gel permeation chromatography (conventional GPC)

The chromatographic system consisted of a PolymerChar GPC-IR (balenkia spain) high temperature GPC chromatograph equipped with an internal IR5 infrared detector (IR 5). The autosampler oven chamber was set at 160 ℃ and the column chamber at 150 ℃. The column used was a 30cm 20 micron linear Mixed bed of 4 Agilent "Mixed A". The chromatographic solvent used was 1,2, 4-trichlorobenzene and contained 200ppm of Butylated Hydroxytoluene (BHT). The solvent source was sparged with nitrogen. The injection volume used was 200 microliters and the flow rate was 1.0 milliliters/minute.

Calibration of the GPC column set was performed with at least 20 narrow molecular weight distribution polystyrene standards, varying in molecular weight from 580 to 8,400,000g/mol, arranged in 6 "cocktail" mixtures with at least ten times the separation between individual molecular weights. The standards were purchased from Agilent technologies, Inc. For molecular weights equal to or greater than 1,000,000g/mol, polystyrene standards were prepared at 0.025 grams in 50 milliliters of solvent, and for molecular weights less than 1,000,000g/mol, polystyrene standards were prepared at 0.05 grams in 50 milliliters of solvent. The polystyrene standards were dissolved at 80 ℃ with gentle stirring for 30 minutes. The molecular weight of the polystyrene standard peaks was converted to the molecular weight of the vinyl polymer using equation 6 (as described by Williams and Ward in polymer science journal: polymer review (j.polym.sci., polym.let.), 6,621 (1968)):

M_polyethylene＝A×(M_Polystyrene)^B(equation 6)

Where M is the molecular weight, A has a value of 0.4315, and B is equal to 1.0.

A fifth order polynomial was used to fit the corresponding ethylene-based polymer-equivalent calibration points. A was adjusted very little (from about 0.39 to 0.44) to correct for column resolution and band spreading effects to obtain NIST standard NBS 1475 at a molecular weight of 52,000 g/mol.

Plate counts of the GPC column set were performed with eicosane (0.04 g prepared in 50ml TCB and dissolved for 20 minutes with slow stirring). Plate count (equation 7) and symmetry (equation 8) were measured at 200 μ l injection according to the following equations:

where RV is the retention volume in milliliters, the peak width in milliliters, the peak maximum is the maximum height of the peak, and the half height is half the height of the peak maximum.

Wherein RV is the retention volume in milliliters and the peak width is in milliliters, the peak maximum is the maximum position of the peak, one tenth the height is one tenth of the height of the peak maximum, and wherein the posterior peak refers to the tail of the peak where the retention volume is later than the peak maximum, and wherein the anterior peak refers to the retention volume earlier than the peak where the peak is the maximum. The plate count of the chromatography system should be greater than 22,000 and the degree of symmetry should be between 0.98 and 1.22.

The samples were prepared in a semi-automated fashion using PolymerChar "Instrument Control" software, with the target weight of the sample set at 2mg/ml, and the solvent (containing 200ppm BHT) was added by a PolymerChar high temperature autosampler to a pre-nitrogen sparged vial capped with a septum. The sample was dissolved at 160 ℃ for 3 hours with "low speed" shaking.

PolymerChar GPCOne was used based on GPC results using an internal IR5 detector (measurement channel) of a PolymerChar GPC-IR chromatograph according to equations 9-12^TMSoftware, data collection points I (IR) at each equal interval_i) Baseline-subtracted IR chromatogram of (g) and ethylenic polymer equivalent molecular weight (M) obtained from a narrow standard calibration curve at point i according to equation 6_{Polyethylene, i}In g/mol) to M_n(GPC)、M_w(GPC)And M_z(GPC)And (4) calculating. Subsequently, a GPC molecular weight distribution (GPC-MWD) plot (wt) of the ethylene-based polymer sample can be obtained_GPC(lgMW) plotting lgMW, wt_GPC(lgMW) is the weight fraction of vinyl polymer molecules with molecular weight lgMW). Molecular weight in g/mol, and wt_GPC(lgMW) follows equation 9.

∫wt_GPC(lgMW) d lg MW ═ 1.00 (Eq. 9)

Number average molecular weight M_n(GPC)Weight average molecular weight M_w(GPC)And z average molecular weight M_z(GPC)Can be calculated as follows.

To monitor the deviation over time, by means of poledA micropump controlled by the ymeerchar GPC-IR system introduced the flow rate marker (decane) into each sample. This flow rate marker (FM) was used to linearly correct the pump flow rate (nominal)) for each sample by comparing the RV of the corresponding decane peak within the sample (RV (FM sample)) to the RV of the alkane peak within the narrow standard calibration (RV (FM calibrated)). Then, it was assumed that any change in decane marker peak time was related to a linear change in flow rate (effective)) throughout the run. To facilitate the highest accuracy of RV measurements of the flow marker peaks, the peaks of the flow marker concentration chromatogram were fitted to a quadratic equation using a least squares fitting routine. The first derivative of the quadratic equation is then used to solve for the true peak position. After calibrating the system based on the flow marker peak, the effective flow rate (calibrated against a narrow standard) is calculated as in equation 13. The flow marker peak was processed by PolymerChar GPCOne^TMAnd (4) completing by software. An acceptable flow rate correction should be such that the effective flow rate should be within 0.5% of the nominal flow rate.

Flow rate_{Is effective}Rate of flow_{Nominal scale}×(RV(FM_{Is calibrated})/(RV(FM_{Sample (I)}) Equation 13)

IR5 GPC comonomer content (GPC-CC) mapping

Calibration of the IR5 detector calibration (using 13C NMR analysis to determine the comonomer content of the reference material according to techniques described in, for example, U.S. Pat. No. 5,292,845 (Kawasaki et al) and J.C. Randall, chemical physical review of macromolecules (Rev.Macromol. chem. Phys.), C29,201-317, which are incorporated herein by reference) was performed using at least ten ethylene-based polymer standards of known Short Chain Branching (SCB) frequency (ethylene-based polymer homopolymer and ethylene/octene copolymer), where total C equals the carbons in the backbone plus the carbons in the branches. Each standard has a weight average molecular weight of 36,000 g/mole to 126,000 g/mole, as determined by GPC, and has a molecular weight distribution of 2.0 to 2.5. Typical copolymer standard properties and measurements are shown in table a.

Table a: "copolymer" standards

An "IR 5 area ratio of" baseline-subtracted area response of IR5 methyl channel sensor "to" baseline-subtracted area response of IR5 measurement channel sensor "(or" IR5 ") was calculated for each of the" copolymer "standards_{Area of methyl channel}/IR5_{Measuring channel area}"" (containing standard filters and filter wheels supplied by PolymerChar (part number IR5 — FWM01) as part of the GPC-IR instrument). A linear fit of Wt% comonomer to "IR 5 area ratio" was constructed in the form of equation 14 below:

weight percent of co-monomer (A)₀+[A₁(IR5_{Area of methyl channel}/IR5_{Measuring channel area})](equation 14)

Thus, a GPC-CC (GPC-comonomer content) plot (wt% comonomer versus lgMW) can be obtained. If there is significant spectral overlap with the comonomer capping (methyl) by the molecular weight determined at each chromatographic slice (slice), end group correction can be made on the wt% comonomer data by knowledge of the capping mechanism.

Crystallization Elution Fractionation (CEF)

Comonomer distribution analysis, also commonly referred to as Short Chain Branching Distribution (SCBD), was measured using a Crystallization Elution Fractionation (CEF) (PolymerChar, spain) equipped with an IR (IR-4 or IR-5) detector (PolymerChar, spain) and a 2-angle light scattering detector model 2040 (Precision Detectors, currently agilent technologies), Monrabal et al, "macromolecules symposium proceedings (macromol. symp.), 257,71-79(2007), which is incorporated herein by reference). Distilled anhydrous ortho-dichlorobenzene (ODCB) was used as solvent with 600ppm of antioxidant Butylated Hydroxytoluene (BHT). For having N₂Blowing-capable autosampler, without BHT. GPC protection column (20 or 10 microns, 50 × 7.5.5 mm) (Agilent technologies) mounted right in the detector oven for IR detectionBefore the device. Sample preparation was performed with an autosampler at 160 ℃ for 2 hours at 4mg/ml (unless otherwise specified) under shaking. The injection volume was 300. mu.l. The temperature profile of CEF is: crystallizing at a rate of 3 ℃/minute from 110 ℃ to 30 ℃; heat equilibration at 30 ℃ for 5 minutes; elution was carried out at a rate of 3 ℃ per minute from 30 ℃ to 140 ℃. The flow rate during crystallization was 0.052 ml/min. The flow rate during elution was 0.50 ml/min. Data was collected at one data point/second.

The CEF column was packed by The Dow Chemical Company (The Dow Chemical Company) through a 1/8 inch stainless tube with 125 μm + -6% glass beads (MO-SCI Specialty Products). According to the requirements of the Dow chemical company, MO-SCI specialty products company has performed acid washing on glass beads. The column volume was 2.06 ml. Column temperature calibration was performed by using a mixture of NIST standard reference materials linear ethylene polymer 1475a (1.0mg/ml) and eicosane (2mg/ml) in ODCB. The temperature was calibrated by adjusting the elution heating rate such that the peak temperature of NIST linear ethylene polymer 1475a was 101.0 ℃ and the peak temperature of eicosane was 30.0 ℃. CEF column resolution was calculated using a mixture of NIST linear ethylenic polymer 1475a (1.0mg/ml) and hexadecane (Fluka, purity ≧ 97.0%, 1 mg/ml). Baseline separation of the hexadecane and NIST ethylene based polymer 1475a was achieved. The ratio of the area of the hexadecane (35.0 to 67.0 ℃) to the area of the NIST 1475a (67.0 to 110.0 ℃) was 50 to 50, the amount of soluble fraction at 35.0 ℃ was less than 1.8 wt%. The CEF column resolution is defined in equation 15:

wherein the full width at half maximum is measured in terms of temperature and the resolution is at least 6.0.

The CEF instrument was equipped with an agilent model 20402-angle light scattering detector (Santa Clara, CA) and calibrated for light scattering using a 90-degree signal channel with known homopolymer ethylene-based polymer standards of known molecular weight (approximately 120,000 g/mol). Also for quality response pairs IR (Red)External) detector is calibrated. Molecular weight at each elution Point (M)_w(CEF)) Calculated as a function of elution temperature in the appropriate signal-to-noise ratio region. Area calculations (total area representing 90 degree light scattering signal divided by the corresponding IR area and multiplied by a factor corresponding to the detector constant) were used to estimate the weight average molecular weight across the elution temperature region and to obtain a CEF-MW plot (M)_w(CEF)Versus temperature curve). Area computation has an inherent advantage of signal-to-noise ratio compared to continuous computation. Both IR and LS (light scattering) signals are subtracted from the baseline signal level according to conventional chromatographic integration techniques.

"critical temperature (T) of the polymer_{Critical point of}) ", weight fraction and weight average molecular weight (at 20 ℃ and T) in a temperature range up to and including the critical temperature_{Critical point of}M of CEF fraction in between_w(CEF)) The calculation of (a) is obtained as follows:

in the case of a temperature increase gradient of 0.2 deg.C, a weight fraction (wt) at each temperature (T) of 20.0 deg.C to 119.9 deg.C is used_CEF(T)) to obtain a CEF-SCBD (CEF-short chain branching distribution) plot, wherein

The critical temperature is defined by the density of the resin (in g/cc) according to:

T_{critical point of}(° c) 1108.1(° c cc/g) × density (g/cc) -952.1(° c) (equation 17)

Calculated at 20 ℃ and T according to CEF-SCBD_{Critical point of}CEF weight fraction between:

similarly, the weight average molecular weight (at 20 ℃ and T) of the fraction from 20 ℃ up to the critical temperature (including the critical temperature)_{Critical point of}M of CEF fraction in between_w(CEF)) Is calculated as: the sum of the 90 degree light scattering responses divided by the sum of the responses at 20 ℃ and T_{Critical point of}By the sum of the IR detector responses and multiplyingA factor calibrated detector constant. In that

Molecular weight calculations and calibrations were performed in the software.

Numerical deconvolution of bivariate data

Obtaining densities, molecular weights and melt indices (I) of the first ethylene-based component, the second ethylene-based component and the third ethylene-based component using numerical deconvolution of bivariate data₂). Using Microsoft Windows

Solver (Solver) (2013) performs a combined CEF-SCBD (wt from CEF)_CEF(T) plot of temperature (T) and GPC-MWD (wt from conventional GPC)_GPC(lgMW)) plotted against lgMW). For CEF-SCBD, the calculated weight fraction (wt) obtained using the method described in the CEF section (in the range of about 23 to 120 ℃)_{Sum, CEF}(T)) is reduced to about 200 equally spaced data points for temperature (T) data to strike a balance between proper iteration speed and temperature resolution. The single or series (up to 3 peaks per component) of exponentially modified Gaussian distributions are summed (equation 19) to represent each component (wt)_C,CEF(T)), and summing the components to give the total weight (wt) at any temperature (T)_{Sum, CEF}(T)), as shown in equations 20A-D.

Wherein C means component (C ═ 1,2, or 3), P means peak (P ═ 1,2, or 3), a_0,C,PChromatographic area of the P-th peak of the C-th component in units of DEG C, a_1,C,PIs the center of the peak of the P-th peak of the C-th component in DEG C, a_2,C,PThe peak width of the No. P peak of the No. C component in units of DEG C, a_3,C,PThe peak tail of the pth peak of the C-th component in units of ° C, and T is the elution temperature in units of ° C. Case of CEF-SCBD for representing Components in a Single exponential modified Gaussian distributionUnder the condition of y_T,C,2＝y _T,C,30. In the case of two exponentially modified Gaussian distributions for CEF-SCBD representing components, only y_T,C,3＝0。

wt_{Sum, CEF}(T)＝wt_C1，CEF(T)+wt_C2，CEF(T)+wt_C3，CEF(T) (Eq. 20D)

Weight fraction (wf) of each component from CEF-SCBD deconvolution_C,CEF) Can be represented by:

wf_C1,CEF＝∫wt_C1(T) dT (Eq. 21A)

wf_C2,CEF＝∫wt_C2(T) dT (equation 21B)

wf_C3,CEF＝∫wt_C3(T) dT (equation 21C)

∫wt_{Sum, CEF}(T) dT ═ 1.00 (equation 21D)

Wherein wf_C1,CEFIs the weight fraction of the first ethylene component, wf, obtained from the deconvolution of CEF-SCBD_C2,CEFIs the weight fraction of the second ethylene-based component, wf, obtained from the deconvolution of CEF-SCBD_C3,CEFIs the weight fraction of the third olefinic component obtained by deconvolution of CEF-SCBD, and the sum of the fractions is normalized to 1.00.

For GPC-MWD, the MWD obtained from the conventional GPC description was imported into the same spreadsheet in 0.01lg (MW/(g/mol)) increments (501 data points total) between 2.00 and 7.00. The following equation shows the molecular weight at weight average M_{w, target}And a polydispersity (M)_w/M_n) Flory-Schulz distribution in the case of 2.0.

lg(M_i+1/(g/mol))-lg(M_i/(g/mol)) ═ 0.01 (equation 24)

In which wt_F-S,iIs at lg (M)_i/(g/mol))(M_iIn g/mol), i is an integer in the range of 0 to 500 to represent each data point on a GPC-MWD plot, and corresponding lg (M)_i/(g/mol)) was 2+0.01 × i.

Then, the voltage is applied to each lg (M)_i/(g/mol)) broadens the Flory-Schulz distribution. At lg (M)_i/(g/mol)) the weight fraction of the normal distribution with a peak remains the same as the original Flory-Schulz distribution. The broadened Flory-Schulz distribution curve can be described by the following equation.

In which wt_GPC(lg(M_iV (g/mol))) is in lg (M)_iV (g/mol)), j is an integer in the range of 0 to 500, and σ is the standard deviation of a normal distribution. Therefore, the molecular weight distribution curves of all three components can be expressed by the following equations. The number average molecular weight (M) can be calculated from the broadened Flory-Schulz_n(GPC)) Weight average molecular weight (M)_w(GPC)) And MWD (M)_w(GPC)/M_n(GPC))。

Where σ is a normal distribution width parameter, and subscripts C1, C2, and C3 represent the first ethylene-based component, the second ethylene-based component, and the third ethylene-based component, respectively. wf_C1,GPC、wf_C2,GPCAnd wf_C3,GPCThe weight fractions from the GPC-MWD of the first ethylene-based component, the second ethylene-based component and the third ethylene-based component, respectively.

Each of the pairs of components from CEF-SCBD and GPC-MWD (first ethylene component (C1), second ethylene component (C2), and third ethylene component (C3)) is considered to be of equivalent mass for its respective technology, as shown in equations 27A-E.

wf_C1,CEF+wf_C2,CEF+wf_C3,CEFAs 1.00 (equation 27A)

wf_C1,GPC+wf_C2,GPC+wf_C3,GPCAs 1.00 (equation 27B)

wf_C1,CEF＝wf_C1,GPC(equation 27C)

wf_C2,CEF＝wf_C2,GPC(equation 27D)

wf_C2,CEF＝wf_C2,GPC(equation 27E)

The process and catalyst data (including catalyst efficiency and reactor mass balance) can be used to initially estimate the relative weight yields of each component. Alternatively, the initial estimates of the weight fraction of each component may be compared by integrating the local region of the CEF-SCBD or GPC-MWD plot of multimodal ethylene polymers (especially noting the visible region with defined peaks or peak inflection points). For example, if the separation is good, the peak area of each component in the CEF-SCBD curve (comparative Polymer 7) can be estimated by dropping the vertical line between the peaks shown in FIG. 3. The correlation of molecular weight order to initial estimates of molecular weight can be obtained from peak positions of the regions of the correlated component in the CEF-SCBD and CEF-MW plots, and should be expected to be consistent with GPC-CC measurements, as shown in FIG. 3. In some cases, initial assignments of peak areas and compositions can be obtained from multimodal GPC-MWD as a starting point and verified under CEF-SCBD and CEF-MW plots.

Initial estimates of peak width and tail for each component in the CEF-SCBD can be obtained by calibrating peak width versus temperature using a series of standard single-site samples such as those previously presented in Table A.

Microsoft

The solver is programmed to minimize the combination of: wt. of_{Sum of GPC}(lgM_i) The sum of the squares of the residuals between and the measured GPC-MWD; and wt_{Sum, CEF}The sum of the squares of the residuals between (T) and the measured CEF-SCBD (where the sampling widths and areas of the two observed distributions are normalized with respect to each other). When the GPC-MWD and CEF-SCBD fits converge at the same time, they are given equal weights. Initial estimates of weight fraction and peak width in CEF-SCBD and molecular weight target for each component were used to get Microsoft Windows

The solver begins as described herein.

The co-crystallization effect of distorting peak shape in CEF was compensated by using Exponentially Modified Gaussian (EMG) peak fitting and in extreme cases by using multiple (up to 3) EMG peaks added to describe a single component. The components produced by the single-site catalyst can be modeled by a single EMG peak. The components produced by the Ziegler-Natta catalyst can be modeled by 1,2 or 3 EMG peaks or a single EMG peak with a long cryogenically-facing tail sufficient to satisfy the extremely high density, extremely low molecular weight target Ziegler-Natta component on a CEF-SCBD plot. In all cases, only a single broadened Flory-Schulz distribution (equations 26A-C) was used, and weight fractions were assigned as the relative sum of one or more of the EMG components from the CEF-SCBD model (equations 27A-E).

For theGPC deconvolution of first and second ethylene-based components prepared by single-site catalysts is subject to the Normal distribution Width parameter (σ) from equations 26A, 26B_C1Or σ_C2The normal distribution width parameter is between 0.000 and 0.170 (corresponding to a polydispersity of about 2.00 to 2.33). In these cases, for the third ethylenic component, M in equation 22_{w, target}Is limited to the lowest because its goal is to be the lowest according to this particular reaction scheme. Note that it is not defined as being limited to the lowest, where possible, depending on the desired performance objectives of the blend within the combined resin reactor. On CEF-SCBD plot (wt)_CEF(T) vs. temperature Curve) at which component peaks of the first ethylene-based component and the second ethylene-based component are observed, by CEF-MW plot (M)_w(CEF)Temperature curve) of M_w(CEF)Two weight average molecular weights (M) of the first ethylene-based component and the second ethylene-based component were observed_w,Target) Ranking (preliminary evaluation). Thus, the order of the molecular weights of the three components is well known. The reactor mass balance yields the mass percent of the third ethylenic component (Wf) of equation 26C, or alternatively, can be calculated by deconvolution using equation 26D (depending on the intensity of the known distribution model of CEF and GPC), and the total weight fraction must add up to 1 (equations 27A-E).

In general, it has been found that

Approximately 20 solver iterations will generally converge well on the solution. If the order of the CEF-MW plotted peaks does not agree for the measured molecular weight with the observed comonomer wt% measurement as measured by GPC-CC, the data must be reconciled by either altering the iteration start point (temperature or lgMW) or slightly changing the width and tail factors in Excel so that the iteration will continue to converge to a consistent solution between the measurements, or the resolution of the measurement must be increased, or additional peaks may be added to the CEF-SCBD to better approximate the elution peak shape of the individual components. If such components are prepared separately, the components may be established a priori by several EMG distributionsAnd (5) molding. FIG. 3 (comparative Polymer 7) shows the high resolution of CEF-SCBD and the lower resolution of GPC-MWD in terms of peak separation, where the ordering and weight fraction measured using LS and IR ratio methods allows excellent iterative convergence on the combined solution. In this case, the higher density species (the third vinyl component) can be modeled by the sum of 2 EMG peaks, the lowest density peak at 30 ℃ (which is attributed to the soluble fraction) can be modeled by the sum of 2 carefully separated EMG peaks, and each intermediate component can be modeled from a single EMG peak. FIG. 4 (inventive Polymer 4) shows an example of acceptable convergence of a very high density low molecular weight component made using a Ziegler-Natta catalyst with two medium density components (made by two different single site catalysts), each using a single peak.

In addition, a predicted M for a CEF-MW can be generated by using the weight average molecular weight of the GPC-MWD of each of the components multiplied by the weight fraction of each of the components observed at each point along the CEF-SCBD plot_w(CEF)And (6) responding. Predicted M_w(CEF)M required to be measured in a CEF-MW plot_w(CEF)And (5) the consistency is achieved. Measured M of individual components from CEF-MW and CEF-SCBD plots can also be used by plotting comonomer incorporation as a function of elution temperature based on a series of known copolymer standards_w(CEF)And comonomer incorporation to predict GPC-CC mapping. The predicted GPC-CC mapping needs to be consistent with the measured GPC-CC.

Peak temperature dependence on density for CEF-SCBD data was obtained using a series of linear ethylene-based polymer standard resins polymerized from a single-site catalyst having a melt index (I)₂) About 1g/10min, or a nominal weight average molecular weight of about 105,000g/mol by GPC, and a polydispersity (or MWD) of less than 2.3 by GPC. At least 10 standard resins of known comonomer content, density and molecular weight in the density range of 0.87g/cc to 0.96g/cc are used. The peak temperature and density data were fitted to a polynomial curve of order 5 to obtain a calibration curve.

The peak width and tail to peak temperature correlations were similarly obtained by fitting the peak width and tail to temperature of the above resins to a linear line, which is very useful for initial estimation in the deconvolution process.

In the inventive resins presented herein, the deconvolution plot directly from the CEF-SCBD represents the first ethylene-based component and the second ethylene-based component as the first two peaks between 35 ℃ and 90 ℃ elution temperature. Using a calibration curve of peak temperature versus density, the "raw density" (density) is calculated from these observed peak positions_Original). Density is determined by using equation 28_OriginalCorrected (in g/cc) to density taking into account the contribution of molecular weight (in g/mol)_{Reality (reality)}(in g/cc):

density of_{Reality (reality)}Density (x ═ density)_Original-0.254g/cc×[lg(M_w(GPC)/(g/mol))-5.02](equation 28)

Wherein M is_w(GPC)Is the weight average molecular weight of the single component deconvoluted from the GPC-MWD.

May be based on the known density of the resin, the density of the first ethylene-based component_{Reality (reality)}Density of the second ethylene-based component_{Reality (reality)}And weight fraction of each component, the density of the third vinyl component is calculated according to the following equation 29.

Melt index (I) of each ethylene component₂) Can be estimated from its weight average molecular weight by the following equation:

lg(I₂/(g/10min))＝-3.759×lg(M_w(GPC)/(g/mol)) +18.9 (equation 30)

Wherein M is_w(GPC)Is the weight average molecular weight (in g/mol) of the single component deconvoluted from the GPC-MWD curve, and I₂Is the melt index (in g/10 min). Note that the amount of long chain branching can vary the coefficients.

Furthermore, to determine the product composition, a single reactor with a single catalyst was sampled directly under the same reactor conditions, a first reactor was sampled for a series two-reactor configuration orSampling two reactors in a parallel dual reactor configuration can be used to help determine the density, melt index (I) of each individual component of a multimodal ethylene-based polymer₂) GPC-MWD, and CEF-SCBD, especially when the reaction is effectively terminated after the sampling point. This allows better confirmation in the case where the peak positions of the first ethylene-based component and the second ethylene-based component cannot be sufficiently determined from the 3-component mixture.

Direct inspection and quantification by analytical cross-fractionation in GPC-TREF (as in PolymerChar CFC units equipped with in-line light scattering (valencia, spain)) and with similar calibrations and calibration of density dependence in bivariate space representing SCBD and molecular weight can also be used to measure the amount of or more accurately distinguish each of the components, particularly for initial estimation, or in cases where high co-crystallization or low resolution/differentiation of the material can be produced, particularly in MWD and SCBD space. (Development of automatic Cross-fractionation equipment (TREF-GPC) for fully characterizing the Bivariate distribution of Polyolefins (Development of an Automated Cross-fractionation apparatus (TREF-GPC)) for a Full Characterisation of the Bivariate distribution. polyolefin Characterization. macromolecular research Collection (macromolecular molecular Symposia), Vol. 257, 2007, pp. 13 to 28. A. Ort ion n, B. Monrabal, J. Sancho-Tello). Sufficient resolution must be obtained in both lgMW and temperature space and should be verified by direct composition ratio methods (e.g., IR-5) and light scattering molecular weight measurements. See Characterization of the Chemical Composition along the Molar Mass distribution in Polyolefin Copolymers by GPC Using Modern Filter-Based IR detectors (Characterization of Chemical Composition of the molecular Mass distribution polymer by GPC Using a model Filter-Based IR Detector) Characterization of polyolefins-Characterization of the ICPC2012 macromolecules symposium (Polyolefin Characterization-ICPC2012Macromolecular Symposia) volume 330, 2013, pages 63 to 80, a.

P.del Hierro,B.Monrabal,J.R.Torres-

M.C.García-

-Coque. Deconvolution of components must use a similar set of equations and similar calibrations examined by a series of single-site resins and resin blends.

Dart strength

The film dart drop test determines the energy that results in failure of a plastic film under the impact conditions of a given free-falling dart. The test result is the energy, expressed as the weight of the projectile dropped from the specified height, that would cause 50% of the tested samples to fail.

Dart impact strength (dart drop strength) was measured according to ASTM D1709 method A, drop height was 26 inches. + -. 0.4 inches (66 cm. + -.1 cm), and the diameter of the polished hemispherical aluminum head was 38.10. + -. 0.13 mm.

Secant modulus

The film MD (machine direction) 1% secant modulus was determined according to ASTM D882 at a crosshead speed of 20 inches/minute. The sample width was 1 inch and the initial clamp spacing was 4 inches. The reported 1% secant modulus value is the average of five measurements.

Examples of the invention

The following examples illustrate features of the present disclosure, but are not intended to limit the scope of the disclosure.

Commercial polymers used

The polymers used in the examples below are provided in table 1.

TABLE 1

Referring to Table 1 and FIG. 2, inventive Polymer 2 and comparative Polymer 6 both have the same density of 0.926g/cc and therefore have the same T of 74.1 ℃_{Critical point of}. T at 20 ℃ and 74.1 ℃_{Critical value}Temperature betweenIn the degree range (reflected by a straight line), the CEF weight fraction is calculated as the area under the curve in these temperature ranges. The y-axis in fig. 2 is the weight fraction of each temperature (x-axis) from 20.0 ℃ to 119.9 ℃, with a temperature increase gradient of 0.2 ℃. For comparative polymer 2, the CEF weight fraction was 17.5%, whereas the CEF weight fraction of inventive polymer 1 was 37.7%. This indicates that the percentage of the lower density first ethylene-based component in inventive polymer 2 is higher.

Tables 2 and 3 below set forth the densities, melt indices (I) of the first, second and third ethylene component of the multimodal inventive polymers Inv 1-Inv 5 and the comparative multimodal inventive polymers Comp 7-Comp 8₂) Weight average molecular weight (M)_w(GPC)) Number average molecular weight (M)_n(GPC)) MWD, and weight percent. Comparative polymers Comp 1-Comp 3 are available from The Dow Chemical Company of Midland, Mich.

TABLE 2

TABLE 3

1 ═ first ethylenic component

2 ═ second ethylene group component

3-a-triethylene component

^*Density of the third vinyl component calculated according to equation 29

Referring to table 1, comparative polymers 4 and 5 are bimodal ethylene-octene copolymers prepared by solution polymerization in a double loop reactor system with a first catalyst system located in the first reactor and a second catalyst system located in the second reactor. Comparative polymers 4 and 5 are related to first compositions 4 and 6 of the invention from WO/2015/200743, respectively.

Inventive polymer Inv 1-Inv 5 and comparative polymer Comp6-Comp8 were prepared according to the following procedures and based on the reaction conditions reported in tables 4 and 5. The reactors are configured for dual series reactor operation.

In a dual series reactor configuration, the effluent from the first polymerization reactor (containing solvent, monomer, comonomer, hydrogen, catalyst components, and dissolved polymer) exits the first reactor and is added to the second reactor separately from the other feeds into the second reactor. The reactor type may be a full liquid adiabatic Continuous Stirred Tank Reactor (CSTR), or a full liquid non-adiabatic isothermal circulating loop reactor simulating a Continuous Stirred Tank Reactor (CSTR) with heat removal. The final reactor effluent (the second reactor effluent in double series) enters a zone where it is deactivated by the addition and reaction of a suitable reagent (water). At this reactor outlet position, further additives are injected to stabilize the polymer.

After catalyst deactivation and addition of additives, the reactor effluent enters a devolatilization system where the polymer is removed from the non-polymer stream. A non-polymer stream is removed from the system. The separated polymer melt was pelletized and collected.

All of the starting materials (monomers and comonomers) and process solvents (narrow boiling range high purity paraffinic solvents, ISOPAR E) are purified with molecular sieves prior to introduction to the reaction environment. Hydrogen was supplied pressurized at high purity levels and no further purification was performed. The reactor monomer feed stream was pressurized above the reaction pressure by a mechanical compressor. The solvent feed was pressurized above the reaction pressure by a pump. The comonomer feed was pressurized above the reaction pressure by a pump. The individual catalyst components were manually batch diluted with purified solvent to the indicated component concentrations and pressurized above the reaction pressure. All reaction feed streams were measured with mass flow meters and independently controlled with metering pumps.

Independent control of all fresh solvent, monomer, comonomer, hydrogen and catalyst component feeds to each reactor was utilized. The temperature of the total fresh feed stream (solvent, monomer, comonomer and hydrogen) to each reactor was controlled by passing the feed stream through a heat exchanger. The total fresh feed to each polymerization reactor is injected into the reactor at one or more locations. The catalyst components are injected into the polymerization reactor separately from the other feeds. The agitator in the CSTR reactor or a series of static mixing elements in the loop reactor is responsible for the continuous mixing of the reactants. Oil baths (for CSTR reactors) and heat exchangers (for loop reactors) provide fine tuning of reactor temperature control.

For reactors that utilize a single procatalyst in each reactor (e.g., Comp6), one procatalyst component is computer controlled to maintain individual reactor monomer conversions equal to the specified targets. The co-catalyst component for a single main catalyst reactor is fed based on the calculated specified molar ratio to one main catalyst component. For reactors that utilize dual procatalysts in one reactor (e.g., Inv 1-Inv 5 and Comp 7-Comp 8), two calculated variables are controlled: (1) the total mass flow of the main catalyst 1 and the main catalyst 2, and (2) the mass fraction of the main catalyst 1 in the total mass flow of the two main catalysts. The total mass flow of the two procatalysts was computer controlled to maintain the individual reactor monomer conversion at the specified target. The mass fraction of procatalyst 1 is controlled to maintain the relative mass fraction of polymer produced by each catalyst in the separate reactor. The co-catalyst component for a reactor utilizing dual procatalysts is fed based on the calculated specified molar ratio to the total of the two procatalyst components.

For Inv 1-Inv 5 and Comp8, the dual series reactor system consisted of two liquid full adiabatic Continuous Stirred Tank Reactors (CSTRs). For Comp7, the dual series reactor system consisted of one liquid full adiabatic Continuous Stirred Tank Reactor (CSTR) and one liquid full non-adiabatic isothermal circulating loop reactor simulating a Continuous Stirred Tank Reactor (CSTR) with heat removal. An adiabatic CSTR is the second reactor. Comparative polymer 6(Comp6) is a bimodal ethylene-octene copolymer prepared by solution polymerization in a double loop reactor system with a first catalyst system in the first reactor and a second catalyst system in the second reactor. The comparative polymer was prepared under similar conditions as disclosed in WO/2015/200743 for the production of the first composition 7 of the invention. Reactor conditions are contained in table 5. The double series reactor system consists of two liquid full non-adiabatic isothermal circulating loop reactors.

TABLE 4

TABLE 5

The formulas of catalyst A, catalyst B and catalyst C used to prepare inventive polymers 1-6 and comparative polymers 7 and 8 are shown below.

Catalyst D was a Ziegler-Natta catalyst. A heterogeneous ziegler-natta type catalyst premix is prepared essentially according to us patent No. 4,612,300 by: to a volume of ISOPAR-E was added a slurry of anhydrous magnesium chloride in ISOPAR-E, EtAlCl, in that order₂Heptane solution of (2) and Ti (O-iPr)₄To obtain a composition having a magnesium concentration of 0.20M and a Mg/Al/Ti ratio of 40/12.5/3. An aliquot of this composition was further diluted with ISOPAR-E to give a final concentration of Ti in the slurry of 500 ppm. The catalyst pre-mix was mixed with triethylaluminium (Et) while being fed to the polymerisation reactor and before entering the polymerisation reactor₃Al) was contacted at the Al to Ti molar ratios specified in tables 4 and 5 to obtain active catalysts. The cocatalyst compositions are listed in table 6 below.

TABLE 6

Description of the invention	Chemical name
		CO-CAT-1	Bis (hydrogenated tallow alkyl) methylammonium tetrakis (pentafluorophenyl) borate (1-)
CO-CAT-2	Branched, cyclic and linear isobutylalumoxanes, methylalumoxane; modified methylaluminoxane
		CO-CAT-3	Et3Al (triethyl aluminum)

Single layer blown film

Collin blown film line was used to make 1 mil blown film. The line included three 25:1L/D single screw extruders equipped with slotted feed zones. The screw diameter was 25mm for the inner layer, 30mm for the core and 25mm for the outer layer. The resins listed in table 1 were added simultaneously to all three extruders to make a single layer film. The annular die had a diameter of 60mm and a double-lip air ring cooling system was used. The die lip gap was 2mm, and the blow-up ratio (BUR) was 2.5. The width of the tile (lay flat) is about 23 to 24 cm. The freeze line height was 5.5 inches. The total output rate was 9 kg/hour (3 kg/hour per extruder). The melting temperature was 210-220 deg.C and the mold temperature was set to 210 deg.C.

TABLE 7

Referring to the results in table 7 and the graph in fig. 1, the inventive sample showed better toughness than the comparative sample. For example, the 1% secant modulus of comparative film 8 is 33,585psi, andthe dart strength value by the A method is 598 g. It is further noted that inventive film 1 comprises a first ethylenic component having a weight percent of 20.58 and has a temperature T at 20 deg.C_{Critical point of}Between CEF weight fraction 23.6%, while comparative film 8 comprises a trimodal polymer having a first ethylenic component of 11.98 wt% and a T at 20 ℃_{Critical point of}A CEF weight fraction of 21.1% between. From a property perspective, the 1% secant modulus of inventive film 1 is approximately 33,952psi (367 psi difference), while the a-process dart drop value of inventive film 1 is 1670g (more than 2.5 times the dart drop value of comparative film 8). This indicates that a trimodal polymer with greater than 20 wt% of the first ethylene-based component achieves a better combination of 1% secant modulus and dart drop strength values. Comparing the comparative films in table 7 with the inventive films, it is evident that the inventive films have a higher combination of 1% secant modulus and dart drop strength values. Referring to fig. 1, the relationship between dart drop strength and 1% secant modulus for inventive films in table 7 can be defined by the following equation:

dart strength (g) > -0.05294(g/psi) > 1% MD secant modulus (psi) +3388(g) (equation 31)

It will be apparent that modifications and variations are possible without departing from the scope of the disclosure defined in the appended claims. More specifically, although some aspects of the present disclosure are identified herein as preferred or particularly advantageous, it is contemplated that the present disclosure is not necessarily limited to these aspects.

Claims (15)

1. A polymer composition, comprising:

at least one multimodal ethylene-based polymer having a density of from 0.900g/cc to 0.940g/cc when measured according to ASTM D792 and a melt index (I) of the at least one multimodal ethylene-based polymer when measured according to ASTM D1238 under a load of 2.16kg and a temperature of 190 ℃₂) From 0.1g/10min to 10g/10min, said multimodal ethylene-based polymer comprising a first ethylene-based component, a second ethylene-based component and a third ethylene-based component, wherein of said first ethylene-based component, said second ethylene-based component and said third ethylene-based componentEach of the ethylene components of (A) is an ethylene monomer and at least one C₃–C₁₂α -the polymerization reaction product of an olefin comonomer, wherein;

the first ethylene-based component has a density of 0.860 to 0.915g/cc, and a weight average molecular weight (M) of the first ethylene-based component_w(GPC)) From 128,000g/mol to 363,000g/mol, the multimodal ethylene-based polymer comprising at least 20 wt% of the first ethylene-based component;

the density of the second ethylene-based component is greater than the density of the first ethylene-based component and less than 0.940g/cc, and the weight average molecular weight (M) of the second ethylene-based component_w(GPC)) Is from 88,500g/mol to 363,000g/mol, and

the density of the third ethylene-based component is greater than the density of the second ethylene-based component.

2. The polymer composition of claim 1, wherein C of the first ethylene-based component₃–C₁₂α -olefin comonomer incorporation of at least 0.5 mol.% and C of the second ethylene-based component₃–C₁₂α -olefin comonomer incorporation was at least 0.5 mol.%.

3. The polymer composition of any of the preceding claims, wherein the multimodal ethylene-based polymer comprises from 20 to 40 wt% of the first ethylene-based component, from 10 to 40 wt% of the second ethylene-based component, from 25 to 60 wt% of the third ethylene-based component.

4. The polymer composition according to any of the preceding claims, wherein the multimodal ethylene-based polymer has a melt index (I)₂) Is 0.3g/10min to 2.0g/10 min.

5. The polymer composition according to any of the preceding claims, wherein I of the multimodal ethylene-based polymer₁₀/I₂A value of 9 to 15, wherein I₁₀Measured according to ASTM D1238 under a load of 10kg and a temperature of 190 ℃.

6. The polymer composition according to any of the preceding claims, wherein the multimodal ethylene-based polymer has a density from 0.910g/cc to 0.940 g/cc.

7. The polymer composition of any of the preceding claims, wherein the density of the first ethylene-based component is from 0.865g/cc to 0.910g/cc and the melt index (I) of the first ethylene-based component₂) Is 0.01g/10min to 0.2g/10 min.

8. The polymer composition of any of the preceding claims, wherein the density of the second ethylene-based component is from 0.880g/cc to 0.930g/cc and the melt index (I) of the second ethylene-based component₂) Is 0.2g/10min to 1.0g/10 min.

9. The polymer composition of any of the preceding claims, wherein the density of the third vinyl component is from 0.935g/cc to 0.965g/cc and weight average molecular weight (M)_w(GPC)) Less than 88,500 g/mol.

10. The polymer composition of any of the preceding claims, wherein C is₃–C₁₂The comonomer is 1-octene or 1-hexene.

11. The polymer composition according to any of the preceding claims, wherein the multimodal ethylene-based polymer has a molecular weight distribution (M)_w(GPC)/M_n(GPC)) Is at least 5, or preferably 5 to 12.

12. The polymer composition of any of the preceding claims, wherein the third ethylenic component has a melt index (I)₂) Is 20g/10min to 750g/10 min.

13. The polymer composition of any preceding claim, wherein the multimodal ethylene-based polymer comprises from 35 to 60 wt% of the third ethylene-based component.

14. The polymer composition of any preceding claim, wherein the multimodal ethylene-based polymer is from 20 ℃ to T_{Critical point of}(T_c) A Crystallization Elution Fraction (CEF) weight fraction of more than 23% and a weight average molecular weight (M)_w(CEF)) Greater than 100,000 g/mol.

15. An article comprising the polymer composition of any of the preceding claims, wherein the article is a blown or cast film.

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